CN106832453A - A kind of Graphene modified natural emulsion material and its preparation method and application - Google Patents
A kind of Graphene modified natural emulsion material and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of Graphene modified natural emulsion material and its preparation method and application, and methods described includes：Grapheme material is mixed with least one auxiliary agent needed for production natural latex products, is ground, obtained mixed material；The mixed material that will be obtained is mixed with natural emulsion, and solidification obtains the Graphene modified natural emulsion material.The present invention is by first being mixed grapheme material with auxiliary agent, avoid adverse effect of the grapheme material to natural emulsion, grapheme material is set preferably to be disperseed, the intensity of reinforcing material, tear-proof degree and anti-microbial property etc. can be used for the preparation of various latex products.
Description
Technical field
The invention belongs to latex product technical field, it is related to a kind of Graphene modified natural emulsion material and preparation method thereof
And application.
Background technology
The features such as natural latex products are due to gas permeability, hygroscopicity, soft touch and high resiliency, by vast use
Like that market scope constantly expands in family.
CN104400956 A disclose a kind of manufacture craft of natural emulsion pillow, comprise the following steps that：Get the raw materials ready mixed
Close, bubble into mould, be heating and curing and punch, equally distributed micropore is formed on latex pillow by needle plate, then again breast
Glue pillow is put into heating chamber, is filled with high-temperature steam, is taken out after 3 minutes and is cleaned and dried, and obtains ventilative latex high
Pillow, but its intensity and anti-microbial property need further raising.
CN102516614 A disclose a kind of n-SiOxModified natural emulsion and preparation method thereof, the method is using natural
Latex based on latex formula emulsion, to make the n-SiOx modified natural emulsions of surface conditioning agent modification through polyol
Mother liquor is modified emulsion, and common working process is carried out to material with ultrasonic wave to shear, and n-SiOx modified natural emulsions are obtained.Should
The latex product quality of natural emulsion production is good, and mechanical performance is significantly improved, but its anti-microbial property needs further raising.
In order to further enhance the performance of natural latex products, its function is expanded, it is proposed that can be in natural latex products
This material with excellent light, electricity, heat and mechanical property and huge specific surface area of Graphene is added in preparation, but
In the prior art, typically all Graphene is combined with natural emulsion first, by obtaining Graphene genuine milk after dispersion
The mixed solution of glue, then carries out the production of downstream product, because natural emulsion exists to conditions such as pH value, the contents of solid content
Particular/special requirement, the pH value of Graphene is likely to result in the solidification of latex, demulsification, so that latex fails, and natural emulsion has
There is certain viscosity, be unfavorable for dispersion of the Graphene in latex.Therefore, how graphene uniform is dispersed in natural emulsion
In, it is the current emphasis studied that the performance of latex can be protected not to be destroyed again.
CN105542248 A disclose a kind of preparation method of Graphene modified natural emulsion, first by Graphene and dispersion
Agent mixed liquor carries out mixed grinding stirring, is then blended into the natural emulsion aqueous solution, adds accelerator, age resistor, vulcanization
Agent and vulcanizing activator, obtain latex mixed liquor；Then enter every trade presulfurization treatment and obtain Graphene modified natural emulsion, though
The right present invention can improve the intensity of natural emulsion composite, but need additionally to add dispersant in the present invention by stone
Black alkene is disperseed.
Therefore, in this area, expect to develop a kind of preparation method of new Graphene composite natral latex product.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of Graphene modified natural emulsion material and its
Preparation method and application.
It is that, up to this purpose, the present invention uses following technical scheme：
On the one hand, the present invention provides a kind of preparation method of Graphene modified natural emulsion material, methods described include with
Lower step：
(1) grapheme material is mixed with least one auxiliary agent needed for production natural latex products, is ground, obtained
Mixed material；
(2) mixed material that step (1) is obtained is mixed with natural emulsion, solidification obtains the modified day of the Graphene
Right latex material.
In the present invention, Graphene is mixed with auxiliary agent first, it is to avoid unfavorable shadow of the Graphene to natural emulsion
Ring, because above-mentioned auxiliary agent needs to be ground in use, Graphene can be made preferably to be disperseed, without additionally adding
Plus can ensure that Graphene obtains fine dispersion in the case of dispersing aid.
In the present invention, the dispersion of Graphene is using the ball mill used in latex product production process, it is not necessary to newly-increased
Equipment, with the grinding distribution that auxiliary agent grinding completes Graphene in same step, has saved processing step, improves operating efficiency,
And the dispersion by auxiliary agent to the dispersion of Graphene and grinding to Graphene during grinding is combined together, can either
Ensure that auxiliary agent, to the dispersion effect of Graphene, while auxiliary agent plays certain protective effect in process of lapping to Graphene, is kept away
Exempt from destruction of the grinding to graphene-structured.
Preferably, the grapheme material is selected from Graphene and its derivative, graphene oxide and its derivative or biology
In matter Graphene and its derivative any one or at least two combination.
Preferably, the Graphene is biomass Graphene.
Wherein, biomass Graphene is to contain single-layer graphene, few layer graphene, graphite with biomass as prepared by raw material
Alkene nano-lamellar structure, and carried metal/nonmetallic compound, the number of plies are not more than 10 layers of two-dimensional nano Carbon Materials, or even can
Be more than on the basis of the carbon composite comprising graphitized charcoal, metal/non-metal compound；The biomass Graphene is also
Including the Graphene by being prepared to biomass resource hydrothermal carbonization method.
Preferably, the biomass Graphene uses the biomass Graphene of Jinan holy well company, i.e., with agriculture and forestry organic waste material
It is primary raw material, the carbon nanomaterial compound containing Graphene obtained by steps such as hydrolysis, catalytic treatment, heat treatments,
It is mainly characterized by containing Graphene, agraphitic carbon and non-carbon nonoxygen element, and the non-carbon nonoxygen element includes Fe, Si and Al unit
Element, the non-carbon nonoxygen element content is the 0.5wt%~6wt% of compound.If number of patent application is 201510819312.X
The product of preparation.The leading indicator of the biomass Graphene it is exemplary can be：Electrical conductivity ＞ 3000S/m, preferably ＞
5000S/m；Specific surface area ＞ 150m2/g, preferably ＞ 300m2/g；Raman spectrum IG/ID ＞ 2, preferably ＞ 3；C/O ＞ 35.0.
Preferably, counted with the weight of natural emulsion as 100%, the consumption of the grapheme material is 0.05~5%, for example
0.05%th, 0.08%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8%, 3%, 3.4%, 3.8%,
4%th, 4.2%, 4.5%, 4.8% or 5%, if the consumption of grapheme material too it is high may due to grapheme material can not be more
Disperse well, and cause Graphene to be reunited, influence the improvement to latex product intensity, and due to there is more Graphene material
Material, can increase influence of the grapheme material to natural emulsion, and then influence the performance of latex product performance.Therefore, using this hair
Bright method, can just be avoided using less grapheme material the latex that the pH value of grapheme material is likely to result in solidification,
The phenomenons such as demulsification.
Preferably, the particle diameter distribution of the grapheme material be D100≤10 μm, such as 10 μm, 9 μm, 8 μm, 7 μm, 6 μm,
5 μm, 4 μm, 3 μm, 2 μm, 1 μm, 0.8 μm, 0.5 μm or 0.3 μm.
Preferably, counted with the weight of natural emulsion as 100%, the consumption of the auxiliary agent is 11~42%, such as 11%,
13%th, 15%, 17%, 20%, 23%, 25%, 28%, 30%, 32%, 34%, 36%, 38% or 42%.
The auxiliary agent refers to compounding agent solution in the present invention, the preferred water of the solvent in the compounding agent solution；Preferably, it is described
The solid content of auxiliary agent be 15~25%, such as 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24% or
25%.
Preferably, the auxiliary agent is any one in vulcanizing agent, setting agent, accelerator or foaming agent or at least two
Combination.
Preferably, the vulcanizing agent includes sulphur and vulcanization accelerator and vulcanized disperse agent.
Preferably, the vulcanization accelerator is 2- benzothiazolyl mercaptans (accelerator M), diethyl-dithio amino
In zinc formate, tetrabenzyl thiuram-disulfide or zinc dibenzyl dithiocarbamate any one or at least two group
Close.
Preferably, the vulcanizing agent also includes surfactant, the preferred oleic acid of surfactant.
Preferably, the setting agent includes prodan and/or magnesium fluosilicate.
Preferably, the setting agent also includes surfactant, the preferred oleic acid of surfactant.
Preferably, the accelerator includes zinc oxide and/or magnesia.
Preferably, the accelerator also includes surfactant, the preferred oleic acid of surfactant.
Preferably, the foaming agent includes oleic acid and/or castor oil.
Preferably, counted with the weight of natural emulsion as 100%, the consumption of the vulcanizing agent is 4~12%, such as 4%,
4.5%th, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%,
11.5% or 12%, preferably 5~8%.
Preferably, counted with the weight of natural emulsion as 100%, the consumption of the setting agent is 3~10%, such as 3%,
3.5%th, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% or 10%, preferably 5
~8%.
Preferably, counted with the weight of natural emulsion as 100%, the consumption of the accelerator is 3~10%, such as 3%,
3.5%th, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% or 10%, preferably 5
~8%.
Preferably, counted with the weight of natural emulsion as 100%, the consumption of the foaming agent is 1~10%, such as 1%,
1.5%th, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%,
9%th, 9.5% or 10%, preferably 3~5%.
Preferably, the time of the grinding is 5~50 hours, such as 5 hours, 8 hours, 10 hours, 13 hours, it is 15 small
When, 18 hours, 20 hours, 23 hours, 25 hours, 28 hours, 30 hours, 32 hours, 35 hours, 38 hours, 40 hours, it is 42 small
When, 45 hours, 48 hours or 50 hours.
In the present invention, the grapheme material can be dividedly in some parts, i.e., preferably, by part graphite in step (1)
Alkene material is mixed with least one auxiliary agent needed for production natural latex products, obtains step (1) in step (2)
Mixed material is mixed with natural emulsion, then adds remaining grapheme material.
Preferably, counted with the weight of natural emulsion as 100%, the consumption of the part grapheme material for 0.03~
2.5%, such as 0.03%, 0.05%, 0.08%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.3% or 2.5%.
Preferably, the particle diameter distribution of the part grapheme material be D100≤1 μm (such as 1 μm, 0.9 μm, 0.8 μm,
0.6 μm, 0.5 μm, 0.4 μm, 0.3 μm, 0.2 μm or 0.1 μm etc.), the particle diameter distribution of the remaining grapheme material for D100≤
10 μm (such as 10 μm, 9 μm, 8 μm, 7 μm, 6 μm, 5 μm, 4 μm, 3 μm, 2 μm, 1 μm, 0.8 μm, 0.5 μm or 0.3 μm).
It is dividedly in some parts by grapheme material, is alleviated because early stage is reunited caused by adding grapheme material excessive；Separately
On the one hand, selection early stage adds grapheme material to add grapheme material particle diameter different with the later stage, because grapheme material grain
The more bad easier reunion of dispersion in footpath, and the relative of big particle diameter will disperse well, so the selection later stage adds the stone of big particle diameter
Black alkene material also causes that Graphene is more beneficial for being uniformly dispersed.
Preferably, when step (1) grapheme material is mixed with the auxiliary agent needed for production natural latex products
Add nano-cellulose.
Preferably, before step (1) grapheme material is mixed with the auxiliary agent needed for production natural latex products,
First grapheme material is mixed with nano-cellulose.
Preferably, the nano-cellulose for natural emulsion quality less than 5%, such as 5%, 4.5%, 4%, 3.5%,
3%th, 2.5%, 2%, 1.8%, 1.5%, 1.3%, 1%, 0.8%, 0.5%, 0.3% or 0.1%, preferably 1~3%.
Preferably, the diameter of the nano-cellulose is within 30nm, such as 30nm, 28nm, 25nm, 20nm, 18nm,
Within 15nm, 13nm, 10nm, 9nm, 8nm, 7nm, 6nm, 5nm, 4nm, 3nm, 2nm or 1nm, preferably 20nm, further preferably
Within 10nm, within more preferably 5nm.
Preferably, the draw ratio of the nano-cellulose is (5-200):1, such as 5:1、8:1、10:1、15:1、18:1、
20:1、25:1、28:1、30:1、35:1、40:1、45:1、50:1、60:1、70:1、80:1、90:1、100:1、120:1、140:
1、160:1、180:1 or 200:1, preferably (10-100):1, more preferably (15-40):1.In the present invention, if nanofiber
The draw ratio of element is excessive, then nano-cellulose can be caused to be difficult to disperse in latex system, or even can make latex strand and fiber
Plain strand is cross-linked with each other and solidifies, if the draw ratio of nano-cellulose is too small, nano-cellulose is to grapheme material
The facilitation of dispersiveness is not obvious.
In the present invention, adding nano-cellulose to mix with grapheme material can utilize the long chain of nano-cellulose
Graphene sheet layer is kept apart, it is to avoid the reunion of Graphene, the enhancing stone additionally, nano-cellulose and Graphene can act synergistically
The intensity and antibiotic effect of black alkene modified natural emulsion material.
Preferably, the nano-cellulose and the mass ratio of grapheme material are (1~5):1, such as 1:1、1.3:1、
1.5:1、1.8:1、2:1、2.3:1、2.5:1、3:1、3.5:1、3.8:1、4:1、4.2:1、4.5:1、4.8:1 or 5:1.Nanowire
Dimension element can cause that grapheme material is fully dispersed with grapheme material under the mass ratio, and work can be cooperateed with again
With significantly increasing the intensity and anti-microbial property of Graphene modified natural emulsion material.
Preferably, if step (1) grapheme material is mixed with a part of auxiliary agent needed for production natural latex products
Close, then the mixed material and other auxiliary agents for obtaining step (1) in step (2) are mixed with natural emulsion.
Preferably, in the grapheme material described in step (1) and at least one auxiliary agent needed for production natural latex products
Before mixing or after mixing, grapheme material is processed using TEMPO systems, until the pH of reaction system is constant or adds
Alcohols material terminating reaction.
In the present invention, the grapheme material dispersive property using the treatment of TEMPO systems is more preferable, even grapheme material
Powder be also easily dispersed in other system solutions.On the one hand passed through using TEMPO System Modification graphite alkenes material
TEMPO systems may be inserted into and bring it about in aggregate swelling, be separated from each other aggregate, be conducive to tending to disperse, if again plus
External force is ground or concussion is more beneficial for it and scatter；On the other hand due to a certain amount of hydroxyl may be contained in graphite alkenes material
Base or the oxygen element existed with other groups, especially graphene oxide or biomass Graphene, oxygen is catalyzed by TEMPO
Change system aoxidizes the oxygen-containing functional group (especially hydroxyl) above graphite alkenes material so that between graphite alkenes material mutually
Strut, and further the graphene layer reunited scatter, and then progressively aoxidize, so on the one hand improve Graphene thing
The chemism on matter surface, on the other hand improves decentralization of the graphite alkenes material in most of solvent (water, alcohol, ketone).
Preferably, the TEMPO systems are the aqueous solution containing TEMPO and/or its derivative, sodium hypochlorite and sodium bromide
System, preferably contains the water solution system of TEMPO, sodium hypochlorite and sodium bromide.
Preferably, the TEMPO derivatives are selected from 2-aza-adamantane-N- epoxides, 1- methyl -2-aza-adamantane-N-
Any one in epoxide, 1,3- dimethyl -2-aza-adamantane-N- epoxides or 4- hydroxyl TEMPO derivatives or at least two
Combination.
Preferably, the pH value of reaction system when being processed grapheme material using TEMPO systems is 2~13,
Such as 2,3,4,5,6,7,8,9,10,11,12 or 13, preferably 3.5~6 or 9.5~11.5, further preferred 10~11.
Preferably, the consumption of the TEMPO and/or its derivative is the 0.05~5% of grapheme material weight, for example
0.05%th, 0.08%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%, preferably 0.1~3%, enter one
Step preferably 0.3~2%, more preferably 0.5~1%.
Preferably, the addition of the sodium hypochlorite is the 10~500% of the grapheme material weight, such as 10%,
30%th, 50%, 80%, 100%, 130%, 150%, 180%, 200%, 230%, 250%, 280%, 300%, 350%,
380%th, 400%, 450%, 480% or 500%, preferably 30~95%, further preferred 40~75%.
Preferably, the addition of the sodium bromide is the 0.5%~50% of the grapheme material weight, such as 0.5%,
0.8%th, 1%, 3%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, preferably 3~30%, further preferred 3~20%,
More preferably 5~10%.
Preferably, the alcohols material is ethanol and/or methyl alcohol.
Used as optimal technical scheme, the preparation method of Graphene modified natural emulsion material of the present invention includes following step
Suddenly：
(1) grapheme material is mixed with the auxiliary agent needed for production natural latex products, with the weight of natural emulsion
It is 100% meter, the consumption of the grapheme material is 0.05~5%, the particle diameter distribution of the Graphene is D100≤10 μm, institute
It is 11~42% to state the consumption of auxiliary agent, and the solid content of the auxiliary agent is 15~25%, is ground 5-50 hours, obtains mixed material；
(2) mixed material that step (1) is obtained is mixed with natural emulsion, is obtained the Graphene modified natural breast
Glue material.
As further preferred technical scheme, the preparation method bag of Graphene modified natural emulsion material of the present invention
Include following steps：
(1) grapheme material is mixed with auxiliary agent and nano-cellulose needed for production natural latex products, with
The weight of natural emulsion is 100% meter, and the consumption of the grapheme material is 0.05~5%, the particle diameter distribution of the Graphene
It is D100≤10 μm, the consumption of the auxiliary agent is 11~42%, the solid content of the auxiliary agent is 15~25%, the nanofiber
Element is less than the 5% of natural emulsion quality, and the nano-cellulose is (1-5) with the mass ratio of Graphene:1,5-50 is small for grinding
When, obtain mixed material；
(2) mixed material that step (1) is obtained is mixed with natural emulsion, is obtained the Graphene modified natural breast
Glue material.
As further preferred technical scheme, the preparation method bag of Graphene modified natural emulsion material of the present invention
Include following steps：
(1) part grapheme material is mixed with least one auxiliary agent needed for production natural latex products, with day
The weight of right latex is 100% meter, and the consumption of the grapheme material is 0.03~2.5%, the particle diameter distribution of the Graphene
It is D100≤1 μm, the consumption of the auxiliary agent is 11~42%, the solid content of the auxiliary agent is 15~25%, is ground 5-50 hours,
Obtain mixed material；
(2) mixed material that step (1) is obtained is mixed with natural emulsion, is then added remaining Graphene material
Material, the particle diameter distribution of the remaining grapheme material is D100≤10 μm, obtains the Graphene modified natural emulsion material.
It is further preferred that the preparation method of Graphene modified natural emulsion material of the present invention is comprised the following steps：
(1) grapheme material is processed using TEMPO systems, until the pH of reaction system is constant or adds alcohols thing
Matter terminating reaction；
(2) by the grapheme material after step (1) treatment and the auxiliary agent and Nanowire needed for production natural latex products
Dimension element is mixed, and is counted with the weight of natural emulsion as 100%, and the consumption of the grapheme material is 0.05~5%, the stone
The particle diameter distribution of black alkene is D100≤10 μm, and the consumption of the auxiliary agent is 11~42%, the solid content of the auxiliary agent for 15~
25%, the nano-cellulose is less than the 5% of natural emulsion quality, and the nano-cellulose is with the mass ratio of Graphene
(1-5):1, grind 5-50 hours, obtain mixed material；
(3) mixed material that step (2) is obtained is mixed with natural emulsion, is obtained the Graphene modified natural breast
Glue material.
On the other hand, the invention provides the Graphene modified natural emulsion material that preparation method as described above is prepared
Material.
On the other hand, the invention provides Graphene modified natural emulsion material as described above in latex product preparation
Application.
Preferably, the latex product includes pillow, mattress, cushion, back cushion, sofa, waist support, shoe-pad, brassiere, automotive seats
Chair, toilet seat pad, condom, gloves, balloon, nipple, feeding bottle or hand warmer.
Graphene modified natural emulsion material of the invention can be made various latex products, and the latex product for obtaining has
Good intensity, wearability is good, excellent corrosion resistance.
Relative to prior art, the invention has the advantages that：
(1) present invention is by first being mixed grapheme material with auxiliary agent, it is to avoid grapheme material is to genuine milk
The adverse effect of glue, because above-mentioned auxiliary agent needs to be ground in use, can be such that grapheme material is preferably divided
Dissipate, there is obvious improvement to the intensity of latex product, using the method for the present invention, using less grapheme material just
The phenomenons such as solidification, the demulsification of latex that the pH value of Graphene is likely to result in can be avoided, and need not be individually to Graphene material
Material carries out decentralized processing.
(2) nano-cellulose is added when grapheme material is mixed with auxiliary agent, it is possible to use the length of nano-cellulose
Strand keeps apart graphene sheet layer, it is to avoid the reunion of Graphene, further enhances the dispersion effect of Graphene, additionally, receiving
Rice cellulose can act synergistically with grapheme material strengthens the intensity and antibiotic effect of Graphene modified natural emulsion material.
(3) the graphene dispersion performance for being processed by TEMPO systems more preferably, further promotes Graphene modified natural emulsion
The performance improvement of material.
Specific embodiment
Technical scheme is further illustrated below by specific embodiment.Those skilled in the art should be bright
, the embodiment be only to aid in understand the present invention, be not construed as to concrete restriction of the invention.
The biomass Graphene applied in following examples can be using the preparation method of biomass Graphene in the prior art
Prepare, such as number of patent application is the technology of 201510819312.X, it would however also be possible to employ the biomass stone of Jinan holy well group production
Black alkene.Other material compositions are available commercially.
Embodiment 1
In the present embodiment, Graphene modified natural emulsion material is prepared by the following method, following steps are specifically included：
(1) biomass Graphene is mixed with the vulcanizing agent needed for production natural latex products, with natural emulsion
Weight is 100% meter, and the consumption of the biomass Graphene is 3%, the particle diameter distribution of the biomass Graphene for D100≤
10 μm, the vulcanizing agent includes sulphur, accelerator M, vulcanized disperse agent, oleic acid and water, and the consumption of vulcanizing agent is 8%, is ground
Mill 48 hours, obtains mixed material；
(2) mixed material and setting agent for obtaining step (1) (are counted, consumption is with the weight of natural emulsion as 100%
5%), accelerator (counted with the weight of natural emulsion as 100%, consumption be 5%) and foaming agent (weight with natural emulsion is
100% meter, consumption is 3%) to be mixed with natural emulsion, obtains the Graphene modified natural emulsion material, wherein all
The solid content sum 26% of auxiliary agent.
Embodiment 2
In the present embodiment, Graphene modified natural emulsion material is prepared by the following method, following steps are specifically included：
(1) biomass Graphene is mixed with the accelerator needed for production natural latex products, with natural emulsion
Weight is 100% meter, and the consumption of the biomass Graphene is 2%, the particle diameter distribution of the biomass Graphene for D100≤
10 μm, the accelerator includes zinc oxide, oleic acid and water, and accelerator dosage is 8%, grinds 36 hours, obtains mixed material；
(2) mixed material and vulcanizing agent for obtaining step (1) (are counted, consumption is with the weight of natural emulsion as 100%
5%), setting agent (counted with the weight of natural emulsion as 100%, consumption be 8%) and foaming agent (weight with natural emulsion is
100% meter, consumption is 5%) to be mixed with natural emulsion, obtains the Graphene modified natural emulsion material, wherein all
The solid content sum of auxiliary agent is 29%.
Embodiment 3
In the present embodiment, Graphene modified natural emulsion material is prepared by the following method, following steps are specifically included：
(1) biomass Graphene is mixed with the setting agent needed for production natural latex products, with natural emulsion
Weight is 100% meter, and the consumption of the biomass Graphene is 2%, the particle diameter distribution of the biomass Graphene for D100≤
10 μm, the setting agent include prodan, bentonite (bentonite can be dispersed into as a form of gel and suspension in aqueous medium, this
Kind of medium solution has certain viscosity, thixotropy and lubricity), oleic acid and water, the consumption of setting agent is 6%, grinding 24
Hour, obtain mixed material；
(2) mixed material and vulcanizing agent for obtaining step (1) (are counted, consumption is with the weight of natural emulsion as 100%
4%), accelerator (counted with the weight of natural emulsion as 100%, consumption be 3%) and foaming agent (weight with natural emulsion is
100% meter, consumption is 1%) to be mixed with natural emulsion, obtains the Graphene modified natural emulsion material, wherein all
The solid content sum of auxiliary agent is 16%.
Embodiment 4
In the present embodiment, Graphene modified natural emulsion material is prepared by the following method, following steps are specifically included：
(1) biomass Graphene is mixed with the auxiliary agent needed for production natural latex products, with the weight of natural emulsion
It is 100% meter to measure, and the consumption of the biomass Graphene is 2%, and the particle diameter distribution of the biomass Graphene is D100≤10 μ
M, the auxiliary agent includes vulcanizing agent, setting agent, accelerator and foaming agent, wherein being counted with the weight of natural emulsion as 100%, vulcanizes
Agent consumption is 5%, and setting agent consumption is 8%, and accelerator dosage is 7%, and foaming agent consumption is 4%, is ground 20 hours, is mixed
Compound material；
(2) mixed material that obtains step (1) and mixed with natural emulsion, obtained the modified day of the Graphene
Right latex material, wherein the solid content sum of all auxiliary agents is 26%.
Embodiment 5
In the present embodiment, Graphene modified natural emulsion material is prepared by the following method, following steps are specifically included：
(1) biomass Graphene is mixed with vulcanizing agent and setting agent needed for production natural latex products, with day
The weight of right latex is 100% meter, and the consumption of the biomass Graphene is 0.5%, the particle diameter point of the biomass Graphene
Cloth is D100≤10 μm, wherein being counted with the weight of natural emulsion as 100%, vulcanizing agent consumption is 12%, and setting agent consumption is
10%, grind 10 hours, obtain mixed material；
(2) mixed material for obtaining step (1) (is counted, consumption is with accelerator with the weight of natural emulsion as 100%
10%) (counted with the weight of natural emulsion as 100%, consumption is 10%) to be mixed with natural emulsion, obtains institute with foaming agent
Graphene modified natural emulsion material is stated, wherein the solid content sum of all auxiliary agents is 42.5%.
Embodiment 6
As different from Example 1, when biomass Graphene is mixed with vulcanizing agent in step (1), nanometer is added
Cellulose, the nano-cellulose is the 3% of natural emulsion quality, and the diameter of the nano-cellulose is described within 30nm
The draw ratio of nano-cellulose is 50:1, remaining preparation method condition is same as Example 1.
Embodiment 7
As different from Example 2, when biomass Graphene is mixed with vulcanizing agent in step (1), nanometer is added
Cellulose, the nano-cellulose is the 2% of natural emulsion quality, and the diameter of the nano-cellulose is described within 20nm
The draw ratio of nano-cellulose is 80:1, remaining preparation method condition is same as Example 2.
Embodiment 8
As different from Example 3, when biomass Graphene is mixed with vulcanizing agent in step (1), nanometer is added
Cellulose, the nano-cellulose is the 5% of natural emulsion quality, and the diameter of the nano-cellulose is described to receive within 5nm
The draw ratio of rice cellulose is 10:1, remaining preparation method condition is same as Example 3.
Embodiment 9
As different from Example 4, when mixed material is mixed with natural emulsion in step (2), Nanowire is added
Dimension element, the nano-cellulose is the 5% of natural emulsion quality, and the diameter of the nano-cellulose is described to receive within 10nm
The draw ratio of rice cellulose is 200:1, remaining preparation method condition is same as Example 4.
Embodiment 10
As different from Example 5, mixed material is carried out with accelerator and foaming agent and natural emulsion in step (2)
During mixing, add nano-cellulose, the 2.5% of the natural emulsion quality of the nano-cellulose, the nano-cellulose it is straight
Within 10nm, the draw ratio of the nano-cellulose is 100 in footpath:1, remaining preparation method condition is same as Example 5.
Embodiment 11
Difference with embodiment 6 is that the draw ratio of the nano-cellulose is 2:1, remaining preparation method condition with
Embodiment 6 is identical.
Embodiment 12
Difference with embodiment 6 is that the draw ratio of the nano-cellulose is 250:1, remaining preparation method condition is equal
It is same as Example 6.
Embodiment 13
Difference from Example 1 is that biomass Graphene was processed with TEMPO systems before step (1),
Until the pH of reaction system is constant to 10, terminating reaction；The TEMPO systems are (to be with grapheme material weight containing TEMPO
100% meter, consumption be 1%), sodium hypochlorite (counted with grapheme material weight as 100%, consumption be 30%) with sodium bromide (with
Grapheme material weight is 100% meter, and consumption is water solution system 10%), and in addition, its preparation method is and embodiment
1 is identical.
Embodiment 14
Difference from Example 2 is that biomass Graphene was processed with TEMPO systems before step (1),
Until the pH of reaction system is constant to 10, terminating reaction；The TEMPO systems are (to be with grapheme material weight containing TEMPO
100% meter, consumption be 0.5%), 75%) and sodium bromide sodium hypochlorite (counted, consumption is with grapheme material weight as 100%
(counted with grapheme material weight as 100%, consumption is water solution system 20%), in addition, its preparation method with reality
Apply example 2 identical.
Embodiment 15
Difference from Example 3 is that biomass Graphene was processed with TEMPO systems before step (1),
Until the pH of reaction system is constant to 10, terminating reaction；The TEMPO systems are (to be with grapheme material weight containing TEMPO
100% meter, consumption be 3%), sodium hypochlorite (counted with grapheme material weight as 100%, consumption be 60%) with sodium bromide (with
Grapheme material weight is 100% meter, and consumption is water solution system 50%), and in addition, its preparation method is and embodiment
3 is identical.
Embodiment 16
Difference from Example 4 is, the biomass Graphene described in step (1) and production natural latex products institute
After the auxiliary agent for needing is mixed, carried out with TEMPO systems to mixture treatment, until the pH of reaction system is constant to 10, terminated
Reaction；The TEMPO systems be containing TEMPO (counted with grapheme material weight as 100%, consumption be 2%), sodium hypochlorite
(counted with grapheme material weight as 100%, consumption is 50%) (to be counted with grapheme material weight as 100%, consumption with sodium bromide
It is water solution system 20%), in addition, its preparation method is same as Example 4.
Embodiment 17
Difference from Example 5 is, the biomass Graphene described in step (1) and production natural latex products institute
After the vulcanizing agent and setting agent for needing are mixed, carried out with TEMPO systems to mixture treatment, until the pH of reaction system is constant
To 10, terminating reaction；The TEMPO systems be containing TEMPO (counted with grapheme material weight as 100%, consumption be 4%),
Sodium hypochlorite (is counted, consumption is 10%) and sodium bromide (is with grapheme material weight with grapheme material weight as 100%
100% meter, consumption is water solution system 5%), and in addition, its preparation method is same as Example 5.
Embodiment 18
Difference from Example 6 is that biomass Graphene was processed with TEMPO systems before step (1),
Until the pH of reaction system is constant to 10, terminating reaction；The TEMPO systems are (to be with grapheme material weight containing TEMPO
100% meter, consumption be 1%), sodium hypochlorite (counted with grapheme material weight as 100%, consumption be 30%) with sodium bromide (with
Grapheme material weight is 100% meter, and consumption is water solution system 10%), and in addition, its preparation method is and embodiment
6 is identical.
Embodiment 19
Difference from Example 7 is that biomass Graphene was processed with TEMPO systems before step (1),
Until the pH of reaction system is constant to 10, terminating reaction；The TEMPO systems are (to be with grapheme material weight containing TEMPO
100% meter, consumption be 0.5%), 75%) and sodium bromide sodium hypochlorite (counted, consumption is with grapheme material weight as 100%
(counted with grapheme material weight as 100%, consumption is water solution system 20%), in addition, its preparation method with reality
Apply example 7 identical.
Embodiment 20
Difference from Example 8 is that biomass Graphene was processed with TEMPO systems before step (1),
Until the pH of reaction system is constant to 10, terminating reaction；The TEMPO systems are (to be with grapheme material weight containing TEMPO
100% meter, consumption be 3%), sodium hypochlorite (counted with grapheme material weight as 100%, consumption be 60%) with sodium bromide (with
Grapheme material weight is 100% meter, and consumption is water solution system 50%), and in addition, its preparation method is and embodiment
8 is identical.
Embodiment 21
Difference from Example 9 is, the biomass Graphene described in step (1) and production natural latex products institute
After the auxiliary agent for needing is mixed, carried out with TEMPO systems to mixture treatment, until the pH of reaction system is constant to 10, terminated
Reaction；The TEMPO systems be containing TEMPO (counted with grapheme material weight as 100%, consumption be 2%), sodium hypochlorite
(counted with grapheme material weight as 100%, consumption is 50%) (to be counted with grapheme material weight as 100%, consumption with sodium bromide
It is water solution system 20%), in addition, its preparation method is same as Example 9.
Embodiment 22
Difference from Example 10 is, the biomass Graphene described in step (1) and production natural latex products
After required vulcanizing agent and setting agent is mixed, carried out with TEMPO systems to mixture treatment, until the pH of reaction system is permanent
Determine to 10, terminating reaction；The TEMPO systems are (to be counted with grapheme material weight as 100%, consumption is containing TEMPO
4%), sodium hypochlorite (is counted, consumption is 10%) and sodium bromide is (with grapheme material weight with grapheme material weight as 100%
It is 100% meter, consumption is water solution system 5%), and in addition, its preparation method is same as in Example 10.
Embodiment 23
Difference from Example 1 is only that, biomass Graphene is replaced with into the hexa-atomic cellulosic material science and technology share in Changzhou
" the model of Co., Ltd's production：The Graphene of SE1231 ".
Embodiment 24
Difference from Example 6 is only that, biomass Graphene is replaced with and is changed to the hexa-atomic cellulosic material science and technology in Changzhou
" the model of limited company's production：The Graphene of SE1231 ".
Embodiment 25
Be the difference is that only with embodiment 13, biomass Graphene is replaced with and is changed to the hexa-atomic cellulosic material science and technology in Changzhou
" the model of limited company's production：The Graphene of SE1231 ".
Embodiment 26
Be the difference is that only with embodiment 18, biomass Graphene is replaced with and is changed to the hexa-atomic cellulosic material science and technology in Changzhou
" the model of limited company's production：The Graphene of SE1231 ".
Embodiment 27
Difference from Example 1 is only that, biomass Graphene is replaced with into graphene oxide.
Embodiment 28
Difference from Example 6 is only that, biomass Graphene is replaced with into graphene oxide.
Embodiment 29
Be the difference is that only with embodiment 13, biomass Graphene is replaced with and is changed to graphene oxide.
Embodiment 30
Be the difference is that only with embodiment 18, biomass Graphene is replaced with and is changed to graphene oxide.
Embodiment 31
In the present embodiment, Graphene modified natural emulsion material is prepared by the following method, following steps are specifically included：
(1) part biological matter Graphene is mixed with the vulcanizing agent needed for production natural latex products, with genuine milk
The weight of glue is 100% meter, and the consumption of the biomass Graphene is 1.5%, and the particle diameter distribution of the biomass Graphene is
D100≤1 μm, the vulcanizing agent includes sulphur, accelerator M, vulcanized disperse agent, oleic acid and water, and the consumption of vulcanizing agent is
8%, grind 48 hours, obtain mixed material；
(2) mixed material and setting agent for obtaining step (1) (are counted, consumption is with the weight of natural emulsion as 100%
5%), accelerator (counted with the weight of natural emulsion as 100%, consumption be 5%) and foaming agent (weight with natural emulsion is
100% meter, consumption is 3%) to be mixed with natural emulsion, and (consumption is 1.5%, particle diameter to add residual biomass Graphene
D100 is distributed as 8 μm) the Graphene modified natural emulsion material is obtained, wherein the solid content sum 26% of all auxiliary agents.
Comparative example 1
The comparative example difference from Example 1 is only that, in preparation process, by grapheme material directly and genuine milk
Glue is mixed, and then adds required auxiliary agent, is ground 48 hours, obtains mixed material, its each Ingredient Amount with embodiment 1
Keep identical.
Comparative example 2
The comparative example difference from Example 6 is only that, in preparation process, by grapheme material directly and genuine milk
Glue is mixed, and then adds nano-cellulose and required auxiliary agent, is ground 48 hours, obtains mixed material, its each Ingredient Amount
Keep identical with embodiment 6.
Comparative example 3
The comparative example the difference is that only with embodiment 18, in preparation process, by grapheme material directly with naturally
Latex is mixed, and then adds nano-cellulose and required auxiliary agent, is ground 48 hours, obtains mixed material, and its each composition is used
Amount keeps identical with embodiment 18.
The Graphene modified natural emulsion material that embodiment 1-30 and comparative example 1-3 are prepared is made thickness and is
The Emulsoid-film of 2mm, tests the intensity and tear-proof degree and antibiotic property of the sample, as a result as shown in table 1.
Table 1
As can be seen from Table 1, grapheme material is mixed with auxiliary agent, it is to avoid grapheme material is to natural emulsion
Adverse effect, and grapheme material can be made preferably to be disperseed, there is obvious improvement to the intensity of latex product,
And cause that latex product has good antibacterial effect.
Applicant state, the present invention illustrated by above-described embodiment Graphene modified natural emulsion material of the invention and
Preparation method, but the invention is not limited in above-described embodiment, that is, do not mean that the present invention has to rely on above-described embodiment ability
Implement.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention, to each raw material of product of the present invention etc.
Effect replacement and addition, selection of concrete mode of auxiliary element etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of preparation method of Graphene modified natural emulsion material, it is characterised in that the described method comprises the following steps：
(1) grapheme material is mixed with least one auxiliary agent needed for production natural latex products, is ground, mixed
Material；
(2) mixed material that step (1) is obtained is mixed with natural emulsion, solidification obtains the Graphene modified natural breast
Glue material.
2. preparation method according to claim 1, it is characterised in that the grapheme material is selected from Graphene and its derivative
In thing, graphene oxide and its derivative or biomass Graphene and its derivative any one or at least two combination；
Preferably, the Graphene is biomass Graphene；
Preferably, counted with the weight of natural emulsion as 100%, the consumption of the grapheme material is 0.05~5%；
Preferably, the particle diameter distribution of the grapheme material is D100≤10 μm.
3. preparation method according to claim 1 and 2, it is characterised in that counted with the weight of natural emulsion as 100%, institute
The consumption for stating auxiliary agent is 11~42%；
Preferably, the solid content of the auxiliary agent is 15~25%；
Preferably, the auxiliary agent is any one in vulcanizing agent, setting agent, accelerator or foaming agent or at least two group
Close；
Preferably, the vulcanizing agent includes sulphur and vulcanization accelerator and vulcanized disperse agent；
Preferably, the vulcanization accelerator is 2- benzothiazolyl mercaptans, zinc diethyl dithiocarbamate, the sulphur of tetrabenzyl two
Change in thiuram or zinc dibenzyl dithiocarbamate any one or at least two combination；
Preferably, the vulcanizing agent also includes surfactant, the preferred oleic acid of surfactant；
Preferably, the setting agent includes prodan and/or magnesium fluosilicate；
Preferably, the setting agent also includes surfactant, the preferred oleic acid of surfactant；
Preferably, the accelerator includes zinc oxide and/or magnesia；
Preferably, the accelerator also includes surfactant, the preferred oleic acid of surfactant；
Preferably, the foaming agent includes oleic acid and/or castor oil；
Preferably, counted with the weight of natural emulsion as 100%, the consumption of the vulcanizing agent is 4~12%, preferably 5~8%；
Preferably, counted with the weight of natural emulsion as 100%, the consumption of the setting agent is 3~10%, preferably 5~8%；
Preferably, counted with the weight of natural emulsion as 100%, the consumption of the accelerator is 3~10%, preferably 5~8%；
Preferably, counted with the weight of natural emulsion as 100%, the consumption of the foaming agent is 1~10%, preferably 3~5%；
Preferably, the time of the grinding is 5~50 hours；
Preferably, part grapheme material is entered with least one auxiliary agent needed for production natural latex products in step (1)
Row mixing, is mixed the mixed material that step (1) is obtained with natural emulsion in step (2), then adds remaining stone
Black alkene material；
Preferably, counted with the weight of natural emulsion as 100%, the consumption of the part grapheme material is 0.03~2.5%；
Preferably, the particle diameter distribution of the part grapheme material is D100≤1 μm, the particle diameter of the remaining grapheme material
It is distributed as D100≤10 μm.
4. the preparation method according to any one of claim 1-3, it is characterised in that in step (1) the Graphene material
Expect to add nano-cellulose when being mixed with the auxiliary agent needed for production natural latex products；
Preferably, before step (1) grapheme material is mixed with the auxiliary agent needed for production natural latex products, first will
Grapheme material mixes with nano-cellulose；
Preferably, nano-cellulose is added when the mixed material that step (1) is obtained is mixed with natural emulsion；
Preferably, the nano-cellulose is less than the 5% of natural emulsion quality, preferably 1~3%；
Preferably, the diameter of the nano-cellulose is within 30nm, within further preferred 10nm, within more preferably 5nm；
Preferably, the draw ratio of the nano-cellulose is (5-200):1, preferably (10-100):1, more preferably (15-
40):1；
Preferably, the nano-cellulose and the mass ratio of grapheme material are (1~5):1；
Preferably, if step (1) grapheme material is mixed with a part of auxiliary agent needed for production natural latex products,
The mixed material and other auxiliary agents for obtaining step (1) in step (2) are mixed with natural emulsion.
5. the preparation method according to any one of claim 1-4, it is characterised in that in the Graphene described in step (1)
Before material mixes with least one auxiliary agent needed for production natural latex products or after mixing, using TEMPO systems to graphite
Alkene material is processed, until the pH of reaction system is constant or adds alcohols material terminating reaction.
6. preparation method according to claim 5, it is characterised in that the TEMPO systems be containing TEMPO and/or its
The water solution system of derivative, sodium hypochlorite and sodium bromide, preferably contains the aqueous solution of TEMPO, sodium hypochlorite and sodium bromide
System；
Preferably, the TEMPO derivatives be selected from 2-aza-adamantane-N- epoxides, 1- methyl -2-aza-adamantane-N- epoxides,
In 1,3- dimethyl -2-aza-adamantane-N- epoxides or 4- hydroxyl TEMPO derivatives any one or at least two group
Close；
Preferably, the pH value of reaction system when being processed grapheme material using TEMPO systems is 2~13, preferably
3.5~6 or 9.5~11.5, further preferred 10~11；
Preferably, the consumption of the TEMPO and/or its derivative for grapheme material weight 0.05~5%, preferably 0.1~
3%, further preferred 0.3~2%, more preferably 0.5~1%；
Preferably, the addition of the sodium hypochlorite is the 10~500% of the grapheme material weight, preferably 30~95%,
Further preferred 40~75%；
Preferably, the addition of the sodium bromide is the 0.5%~50% of the grapheme material weight, preferably 3~30%, enter
One step preferably 3~20%, more preferably 5~10%；
Preferably, the alcohols material is ethanol and/or methyl alcohol.
7. the preparation method according to any one of claim 1-6, it is characterised in that the described method comprises the following steps：
(1) grapheme material is mixed with the auxiliary agent needed for production natural latex products, the weight with natural emulsion is
100% meter, the consumption of the grapheme material is 0.05~5%, and the particle diameter distribution of the Graphene is D100≤10 μm, described
The consumption of auxiliary agent is 11~42%, and the solid content of the auxiliary agent is 15~25%, is ground 5-50 hours, obtains mixed material；
(2) mixed material that step (1) is obtained is mixed with natural emulsion, is obtained the Graphene modified natural emulsion material
Material；
It is further preferred that the described method comprises the following steps：
(1) part grapheme material is mixed with least one auxiliary agent needed for production natural latex products, with genuine milk
The weight of glue is 100% meter, and the consumption of the grapheme material is 0.03~2.5%, and the particle diameter distribution of the Graphene is
D100≤1 μm, the consumption of the auxiliary agent is 11~42%, and the solid content of the auxiliary agent is 15~25%, is ground 5-50 hours, is obtained
To mixed material；
(2) mixed material that step (1) is obtained is mixed with natural emulsion, is then added remaining grapheme material, institute
The particle diameter distribution of remaining grapheme material is stated for D100≤10 μm, the Graphene modified natural emulsion material is obtained.
8. the preparation method according to any one of claim 1-7, it is characterised in that the described method comprises the following steps：
(1) grapheme material is mixed with auxiliary agent and nano-cellulose needed for production natural latex products, with natural
The weight of latex is 100% meter, and the consumption of the grapheme material is 0.05~5%, and the particle diameter distribution of the Graphene is
D100≤10 μm, the consumption of the auxiliary agent is 11~42%, and the solid content of the auxiliary agent is 15~25%, the nano-cellulose
It is less than the 5% of natural emulsion quality, the nano-cellulose is (1-5) with the mass ratio of Graphene:1, grind 5-50 hours,
Obtain mixed material；
(2) mixed material that step (1) is obtained is mixed with natural emulsion, is obtained the Graphene modified natural emulsion material
Material；
It is further preferred that the described method comprises the following steps：
(1) grapheme material is processed using TEMPO systems, until the pH of reaction system is constant or adds alcohols material end
Only react；
(2) by the grapheme material after step (1) treatment and the auxiliary agent and nano-cellulose needed for production natural latex products
Mixed, counted with the weight of natural emulsion as 100%, the consumption of the grapheme material is 0.05~5%, the Graphene
Particle diameter distribution be D100≤10 μm, the consumption of the auxiliary agent is 11~42%, and the solid content of the auxiliary agent is 15~25%, institute
It is less than the 5% of natural emulsion quality to state nano-cellulose, and the nano-cellulose is (1-5) with the mass ratio of Graphene:1,
Grinding 5-50 hours, obtains mixed material；
(3) mixed material that step (2) is obtained is mixed with natural emulsion, is obtained the Graphene modified natural emulsion material
Material.
9. the Graphene modified natural emulsion material that the preparation method according to any one of claim 1-8 is prepared.
10. application of the Graphene modified natural emulsion material according to claim 9 in latex product preparation；
Preferably, the latex product include pillow, mattress, cushion, back cushion, sofa, waist support, shoe-pad, brassiere, automotive seat,
Toilet seat pad, condom, gloves, balloon, nipple, feeding bottle or hand warmer.
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